Summary: Benzoyl peroxide is used as an oxidizing agent for the first time in the synthesis of conducting polypyrrole. Synthesis of polypyrrole is commonly performed by chemical oxidative polymerization using water-soluble oxidizing agents. In this work, polypyrrole was prepared using organic solvent-soluble benzoyl peroxide as an oxidizing agent in the presence of p-toluenesulfonic acid (p-TSA) and sodium lauryl sulfate (SLS) surfactant via the inverted-emulsion-polymerization technique. During polymerization, SLS is converted to dodecyl hydrogensulfate (DHS) and incorporated on to polypyrrole along with p-TSA dopant, indicating SLS is acting as emulsifier as well as dopant. The influence of synthesis conditions such as the duration of the reaction, the temperature, the concentration of the reactants, etc., on the properties of polypyrrole was investigated to determine the optimum conditions for the synthesis of polypyrrole salt. Polypyrrole was obtained in a reaction time of 1 h with high yield (154 wt.-% with respect to pyrrole used) and good conductivity (2 S · cm−1). The conductivity of polypyrrole-salt was found to be nearly the same even after seven months of storage at ambient temperature (1.7 S · cm−1).